JP6020896B2 - Assembled battery - Google Patents

Description

The present invention relates to an assembled battery including a plurality of air batteries. More particularly, the present invention relates to an assembled battery using the air battery Ru bovine reduce internal resistance.

  The air battery is a battery that uses oxygen in the air as an active material, and can be said to be a power source that is economical and can be used without maintenance for a long time. In general, a button type battery having a structure in which a metal negative electrode case and a metal positive electrode case having air holes are fitted via a gasket is known. In the internal space of the case fitting body, a negative electrode, a separator, an air electrode (positive electrode), a water repellent film, and an electrolytic solution are respectively disposed. In such a button type battery, the internal space of the case fitting body is divided by a separator impregnated with an electrolytic solution. One space is filled with zinc to serve as a negative electrode, and the other space is disposed with a catalyst to serve as an air electrode (positive electrode). Further, a water repellent film composed of a polytetrafluoroethylene (PTFE) porous film is disposed on the side opposite to the air electrode side separator.

  In Patent Document 1, a specific treatment is applied to the PTFE porous film constituting the water-repellent film for the purpose of further improving the water removing function of the water-repellent film and extending the life of the button-type battery. It has been proposed (see Patent Document 1).

Patent No. 3034110

  As a result of studying the use of an air battery as an assembled battery by the present inventors, it is possible to construct an assembled battery having sufficient performance only by applying the water-repellent film having excellent water repellency described in Patent Document 1. I found a new problem that I could not do. This problem is caused by an increase in internal resistance in a water repellent film or the like, and is not mentioned at all in Patent Document 1 to which a button type battery is applied.

The present invention has been made to solve such a new problem. The present invention aims at providing a battery pack including a plurality of air cells Ru bovine reduce internal resistance.

An assembled battery according to an aspect of the present invention includes a positive electrode layer, an electrolyte layer stacked on the positive electrode layer, a negative electrode layer stacked on the electrolyte layer, and a positive electrode layer stacked on the positive electrode layer. including a plurality of air cells and a conductive liquid-tight ventilation layer located on the opposite side with. A flow path is provided between the conductive liquid-tight ventilation layer in the first air battery and the negative electrode layer in the second air battery adjacent to the first air battery to distribute the oxygen-containing gas. Yes. Further, the first air battery is electrically connected to the negative electrode layer in the second air battery via the conductive liquid-tight ventilation layer.

FIG. 1 is a cross-sectional view showing a schematic configuration of the assembled battery according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view showing a schematic configuration of an assembled battery according to the second embodiment of the present invention. FIG. 3 is a cross-sectional view showing a schematic configuration of an assembled battery according to the third embodiment of the present invention.

Hereinafter, the battery pack of the present invention, will be described with reference to the drawings in detail. In addition, the dimension ratio of drawing is exaggerated on account of description, and may differ from an actual ratio.

[Air battery]
Air cell 10, as shown in FIG. 1, a negative electrode layer 11, an electrolyte layer 13, a positive electrode layer 12, a structure formed by laminating in this order. And it has the electroconductive liquid-tight ventilation layer 14 laminated | stacked on the positive electrode layer 12, and located in the reverse side to the electrolyte layer 13 with respect to the positive electrode layer 12. FIG. That is, the air battery 10 in FIG. 1 has a configuration in which the positive electrode layer 12 is interposed between the conductive liquid-tight ventilation layer 14 and the electrolyte layer 13. The “conductive liquid-tight ventilation layer” has conductivity and air permeability, and at the same time has a function of blocking movement by blocking liquid, thereby preventing leakage of liquid from the electrolyte layer to the outside. It means a layer having performance. Since the air battery 10 can have a thick conductive path by having the above configuration, the internal resistance can be reduced. In this specification, the “conductive path” is a term that means a path of a current flowing through the air battery. That is, a direction perpendicular to the stacking surface of each layer constituting the air battery of this embodiment is referred to as a “conductive path direction”, and the “conductive path” is a path along this direction.

[Battery]
Moreover, the assembled battery which concerns on one Embodiment of this invention is equipped with two or more above-mentioned air batteries. And the flow path which distribute | circulates oxygen-containing gas interposed between the electroconductive liquid-tight ventilation layer in a 1st air battery and the negative electrode layer in the 2nd air battery adjacent to a 1st air battery is formed. Has been. Further, the first air battery is electrically connected to the negative electrode layer in the second air battery via the conductive liquid-tight ventilation layer. By adopting such a configuration, the internal resistance in the conductive liquid-tight ventilation layer can be reduced and the conductive path can be increased, so that the internal resistance can be reduced. Here, “connection” means both direct connection and parallel connection. And when it is set as series connection, especially a conduction path can be shortened thickly and internal resistance can be reduced more.

Moreover, it is preferable that the assembled battery of this form is provided with a conductive porous body inside the flow path. With such a configuration, the positive electrode layer of the first air battery and the negative electrode layer of another adjacent air battery are electrically connected via the conductive liquid-tight ventilation layer and the conductive porous body in the flow path. Connected to. As a result, the internal resistance can be reduced. Further, a conductive path direction in the layer thickness direction and the battery pack in an air battery, which is preferably configured in a flat row. By setting it as such a structure, the internal resistance in a liquid-tight ventilation layer can be reduced. In addition, the positive electrode layer of the first air battery and the negative electrode layer of another adjacent air battery can be electrically connected via the conductive liquid-tight ventilation layer and the conductive porous body in the flow path. . Thereby, the conductive path can be made thicker and shorter, so that the internal resistance can be further reduced. As a connection mode, series connection is preferable from the above viewpoint.

  Furthermore, in the assembled battery of this embodiment, it is preferable that the conductive liquid-tight ventilation layer is a conductive water-repellent layer having conductivity and water-tight ventilation. In addition, watertight air permeability means the performance to block the aqueous solution and prevent leakage to the outside while having air permeability. By adopting such a configuration, even when an aqueous solution is used as the liquid contained in the electrolyte layer, the internal resistance in the liquid-tight ventilation layer can be reduced. As a result, the conductive path can be made thicker and the internal resistance can be reduced.

  In the assembled battery of this embodiment, the conductive water-repellent layer preferably contains at least one of a water-repellent conductive material and a water-repellent material and a conductive material. By setting it as such a structure, the internal resistance in a liquid-tight ventilation layer can be reduced, without specifically limiting about the form of the electrically conductive material in an electroconductive water repellent layer. As a result, the conductive path can be made thicker and the internal resistance can be reduced.

  Furthermore, in the assembled battery of the present embodiment, it is preferable that the conductive water-repellent layer contains a microporous membrane, a fiber assembly, a fiber structure, or any combination thereof. By setting it as such a structure, the internal resistance in a liquid-tight ventilation layer can be reduced, without specifically limiting about the form of the layer structure of an electroconductive water repellent layer. As a result, the conductive path can be made thicker and the internal resistance can be reduced.

  In the assembled battery of this embodiment, the conductive material preferably contains one or both of a fibrous conductive material and a particulate conductive material. By adopting such a configuration, the internal resistance in the liquid-tight ventilation layer can be reduced regardless of whether the shape of the conductive material is fibrous or particulate. As a result, the conductive path can be made thicker and the internal resistance can be reduced.

  Furthermore, in the assembled battery of this embodiment, it is preferable that the conductive material contains one or both of carbon and metal. By adopting a configuration in which carbon or metal having excellent conductivity is applied, the internal resistance in the liquid-tight ventilation layer can be further reduced. As a result, the conductive path can be made thicker and the internal resistance can be further reduced.

  In the assembled battery of the present embodiment, the water repellent material preferably contains one or both of an olefin resin and a fluorine resin. By adopting a configuration in which an olefin resin or a fluorine resin excellent in water repellency is applied, it is possible to reduce the internal resistance in the liquid tight ventilation layer while suppressing the liquid tightness reduction. As a result, since the conductive path can be made thick, the internal resistance can be reduced.

  Furthermore, in the assembled battery of the present embodiment, the conductive porous body is preferably related to a particle assembly, a fiber assembly, a fiber structure, a porous plate, or any combination thereof. By setting it as such a structure, the internal resistance in a liquid-tight ventilation layer can be reduced. Furthermore, the positive electrode layer of one air battery and the negative electrode layer of another adjacent air battery are electrically connected via the conductive liquid-tight ventilation layer on the positive electrode layer and the conductive porous body in the flow path. be able to. Thereby, the conductive path can be made thicker and shorter, so that the internal resistance can be further reduced. As a connection mode, series connection is preferable from the above viewpoint.

  In the assembled battery of the present embodiment, the conductive porous body preferably contains one or both of carbon and metal. By adopting a configuration in which carbon or metal having excellent conductivity is applied, the internal resistance in the conductive porous body can be further reduced. As a result, the conductive path can be made thicker and the internal resistance can be further reduced.

  Furthermore, in the assembled battery of this embodiment, it is preferable that either one or both of the water-repellent conductive material and the water-repellent material include those obtained by subjecting a non-water-repellent material to a water-repellent treatment. . An example of water repellent treatment is fluorine treatment. This fluorine treatment is not particularly limited, and various conventionally known fluorine treatments may be applied according to the type of the non-water-repellent material. By setting it as such a structure, it is not specifically limited about the material which exhibits water repellency, The internal resistance in a liquid-tight ventilation layer can be reduced. As a result, the conductive path can be made thicker and the internal resistance can be reduced.

  Hereinafter, some embodiments of the present invention will be described in detail with reference to the drawings.

[First Embodiment]
FIG. 1 is a cross-sectional view illustrating a schematic configuration of the assembled battery according to the first embodiment. In addition, the arrow shown in FIG. 1 has shown the conduction path direction.

As shown in FIG. 1, the assembled battery 1 of the present embodiment includes a plurality of the above-described air batteries. The first air battery 10 has a configuration in which a negative electrode layer 11, an electrolyte layer 13, a positive electrode layer 12, and a conductive water-repellent layer 14 which is an example of a conductive liquid-tight ventilation layer are laminated in this order. In addition, the negative electrode layer 11 is laminated on the negative electrode current collecting layer 21. Of course, the second air battery 10 ′ adjacent to the first air battery 10 has the same configuration as the first air battery 10. Note that the first air battery 10 and the second air battery 10 ′ in this example are stacked via the spring 22a and the negative electrode current collecting layer 21 ′ in the second air battery 10 ′. The spring 22 a is an example of a positive electrode current collector, and the negative electrode current collector layers 21, 21 ′, 21 ″ are examples of a negative electrode layer exterior material. Further, the spring 22 a is laminated on the positive electrode layer 12 of the first air battery 10. In addition, a conductive water repellent layer 14 located on the opposite side of the electrolyte layer 13 with respect to the positive electrode layer 12 is provided, that is, the negative electrode in the second air battery 10 ′ via the conductive water repellent layer 14. The current collecting layer 21 ′ and the positive electrode layer 12 are electrically connected to each other, and the conductive water repellent layer 14 laminated on the positive electrode layer 12 of the first air battery 10 and the second A flow path AP through which an oxygen-containing gas flows is formed by the spring 22a and the negative electrode current collecting layer 21 'provided between the negative electrode layer in the air battery 10'. The conductive path can be made thick while ensuring the function as a battery. As a result, the internal resistance can be reduced, and in this embodiment, the conductive water repellent layer 14 provided on the positive electrode layer 12 of the first air battery 10 and the second air battery 10. Although the negative electrode current collecting layer 21 'is provided between the negative electrode layer 11 and the negative electrode layer 11, it is included in the scope of the present invention. However, the present invention is not limited to this, and parallel connection modes are also included in the scope of the present invention.

  Hereinafter, each configuration will be described in more detail.

(Negative electrode layer)
The negative electrode layer 11 includes, for example, a negative electrode active material composed of a single metal or an alloy whose standard electrode potential is lower than that of hydrogen. In some cases, it may be formed of a porous material. Examples of simple metals whose standard electrode potential is lower than hydrogen include, for example, lithium (Li), zinc (Zn), iron (Fe), aluminum (Al), magnesium (Mg), manganese (Mn), silicon (Si), Examples include titanium (Ti), chromium (Cr), and vanadium (V). An alloy can also be applied. In general, an alloy is a generic term for a metal element having one or more metal elements or non-metal elements added and having metallic properties. Specifically, a material obtained by adding one or more metal elements or non-metal elements to the above metal element can be given. It should be noted that the alloy structure includes eutectic alloys in which the component elements are separated into crystals, that is, a mixture of the component elements that are completely melted into a solid solution, and the component elements are composed of intermetallic compounds or metals and nonmetals. Some form a compound. In the present invention, any of the above alloy structures may be used. However, the material is not limited to these, and a conventionally known material applied to the air battery can be applied.

(Positive electrode layer)
The positive electrode layer 12 includes, for example, a catalyst component, a conductive catalyst carrier that supports the catalyst component, and a binder that binds the catalyst component, and has a porous structure. In addition, a catalyst carrier and a binder are contained as needed. Hereinafter, a composite in which a catalyst component is supported on a catalyst carrier is also referred to as an “electrode catalyst”.

  Specific examples of the catalyst component include platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), palladium (Pd), osmium (Os), tungsten (W), lead (Pb), Metals such as iron (Fe), chromium (Cr), cobalt (Co), nickel (Ni), manganese (Mn), vanadium (V), molybdenum (Mo), gallium (Ga) and aluminum (Al), and these An alloy can be selected. Further, the structure of the alloy is as described above.

  The shape and size of the catalyst component are not particularly limited, and the same shape and size as those of conventionally known catalyst components can be employed. However, the shape of the catalyst component is preferably granular. Moreover, it is preferable that the average particle diameter of a catalyst particle is 1-30 nm. When the average particle diameter of the catalyst particles is within such a range, the balance between the catalyst utilization rate and the ease of loading can be appropriately controlled. The catalyst utilization rate is related to the effective electrode area of the electrode surface where the electrochemical reaction proceeds.

  The “average particle diameter of catalyst particles” in the present invention is the average of the crystallite diameter determined from the half-value width of the diffraction peak of the catalyst component in X-ray diffraction or the average particle diameter of the catalyst component determined from a transmission electron microscope image. It can be measured as a value. The catalyst carrier functions as a carrier for supporting the above-described catalyst component, and an electron conduction path involved in the transfer of electrons between the catalyst component and other members. Any catalyst carrier may be used as long as it has a specific surface area for supporting the catalyst component in a desired dispersion state and sufficient electron conductivity, and the main component is preferably carbon. Specific examples of the catalyst carrier include carbon particles made of carbon black, activated carbon, coke, natural graphite, artificial graphite, and the like.

  “The main component is carbon” means that the main component contains carbon atoms, and includes the meanings of “consisting only of carbon atoms” and “substantially consisting of carbon atoms”. is there. Note that “substantially consisting of carbon atoms” means that contamination of about 2 to 3% by mass or less of impurities can be allowed.

The BET specific surface area of the catalyst carrier may be a specific surface area sufficient to carry the catalyst component in a highly dispersed state, and is preferably 20 to 1600 m ² / g, more preferably 80 to 1200 m ² / g. When the specific surface area of the catalyst carrier is within such a range, the balance between the dispersibility of the catalyst component on the catalyst carrier and the effective utilization rate of the catalyst component can be appropriately controlled.

  The size of the catalyst carrier is not particularly limited. From the viewpoints of easy loading, catalyst utilization, and catalyst layer thickness control within an appropriate range, the average particle size of the catalyst carrier is preferably about 5 to 200 nm, and preferably about 10 to 100 nm. In the electrode catalyst, the supported amount of the catalyst component is preferably 10 to 80% by mass, more preferably 30 to 70% by mass, based on the total amount of the electrode catalyst. When the supported amount of the catalyst component is within such a range, the balance between the degree of dispersion of the catalyst component on the catalyst support and the catalyst performance can be appropriately controlled. The amount of the catalyst component supported on the electrode catalyst can be measured by inductively coupled plasma emission spectroscopy (ICP). However, the material is not limited to these, and a conventionally known material applied to the air battery can be applied.

  Further, the binder is not particularly limited, and examples thereof include the following materials. Examples include polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyether nitrile (PEN), polyacrylonitrile (PAN), polyimide (PI), and polyamide (PA). Cellulose, carboxymethyl cellulose (CMC), ethylene-vinyl acetate copolymer, polyvinyl chloride (PVC), styrene / butadiene rubber (SBR), isoprene rubber, butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene Mention may also be made of polymers and styrene / butadiene / styrene block copolymers and their hydrogenated products. Further, thermoplastic polymers such as styrene / isoprene / styrene block copolymer and hydrogenated products thereof, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) ), Tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE) In addition, a fluororesin such as polyvinyl fluoride (PVF) is also included. In addition, vinylidene fluoride-hexafluoropropylene fluororubber (VDF-HFP fluoropolymer), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene fluororubber (VDF-HFP-TFE fluororubber), vinylidene fluoride- Pentafluoropropylene-based fluororubber (VDF-PFP-based fluororubber), vinylidene fluoride-pentafluoropropylene-tetrafluoroethylene-based fluororubber (VDF-PFP-TFE-based fluororubber), vinylidene fluoride-perfluoromethylvinylether-tetra Fluoroethylene fluoro rubber (VDF-PFMVE-TFE fluoro rubber), vinylidene fluoride-chlorotrifluoroethylene fluoro rubber (VDF-CTFE fluoro rubber) ) Vinylidene fluoride-based fluororubber and epoxy resins such as. Among these, polyvinylidene fluoride, polyimide, styrene / butadiene rubber, carboxymethyl cellulose, polypropylene, polytetrafluoroethylene, polyacrylonitrile, and polyamide are more preferable. These binders may be used alone or in combination of two or more.

(Electrolyte layer)
The electrolyte layer 13 includes, for example, an electrolytic solution and, if necessary, a porous separator. As the electrolytic solution, for example, an aqueous solution or non-aqueous solution of potassium chloride, sodium chloride, potassium hydroxide, or the like can be used. However, it is not limited to these, The conventionally well-known electrolyte solution applied to an air battery can be applied. Moreover, the separator can use suitably the microporous film which consists of polyolefin, such as glass paper which has not performed water-repellent treatment, polyethylene, a polypropylene, etc. with respect to the electrolyte solution which is aqueous solution. However, the material is not limited to these, and a conventionally known material applied to the air battery can be applied.

(Conductive liquid tight ventilation layer)
As the conductive liquid-tight ventilation layer 14, for example, a conductive water repellent layer can be suitably used. The conductive water-repellent layer has a water-repellent property that can suppress leakage of the electrolyte contained in the air battery, and has a porous structure that allows gas to flow relatively easily. Furthermore, the conductive water-repellent layer forms a three-phase interface on the positive electrode to improve the reactivity, and at the same time has conductivity and also functions as a conductive path. Examples of such a conductive liquid-tight ventilation layer include a water-repellent conductive material and a material containing a water-repellent material and a conductive material. These can be used alone or in combination of two or more. A typical example of a conductive material having water repellency is a conductive polymer material. A typical example of a material including a water repellent material and a conductive material is a resin in which a conductive filler as a conductive material is added to a conductive polymer material or a non-conductive polymer material.

  Examples of the conductive polymer material include polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polyacrylonitrile, and polyoxadiazole. Such a conductive polymer material has sufficient conductivity without adding a conductive material.

  Examples of the non-conductive polymer material include polyethylene (PE) such as high density polyethylene (HDPE) and low density polyethylene (LDPE), olefin resin such as polypropylene (PP), and polytetrafluoroethylene (PTFE). And fluorine-based resins such as polyvinylidene fluoride (PVdF), polyethylene terephthalate (PET), polyether nitrile (PEN), polyimide (PI), polyamideimide (PAI), polyamide (PA), styrene-butadiene rubber (SBR), Examples thereof include polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), and polystyrene (PS). Such a non-conductive polymer material has excellent potential resistance or solvent resistance. Of these, olefin resins and fluorine resins are preferable.

  A conductive material can be added to the conductive polymer material or the non-conductive polymer material as necessary. In particular, in the case where the resin serving as the base material is composed only of a non-conductive polymer, a conductive material is inevitably necessary to impart conductivity to the resin. The conductive material can be used without particular limitation as long as it is a substance having conductivity. For example, metals, conductive carbon, etc. are mentioned as a material excellent in electroconductivity and electric potential resistance. As metals, nickel (Ni), titanium (Ti), aluminum (Al), copper (Cu), platinum (Pt), iron (Fe), chromium (Cr), tin (Sn), zinc (Zn), indium Preferred examples include those containing at least one metal selected from the group consisting of (In), antimony (Sb), and potassium (K), or an alloy or metal oxide containing these metals.

  In addition, as the conductive carbon, at least one selected from the group consisting of acetylene black, vulcan, black pearl, carbon nanofiber, ketjen black, carbon nanotube, carbon nanohorn, carbon nanoballoon, fullerene, and vapor grown carbon is used. What is contained can be mentioned as a suitable example.

  The shape of the conductive material is not particularly limited, and one type of fibrous conductive material and granular conductive material can be used alone or in combination of two or more types. Further, for example, a conductive repellent obtained by forming a porous conductive layer with a material that can be applied to the above-described conductive polymer material or conductive filler and then performing a water repellent treatment such as a fluorine treatment. An aqueous layer can also be applied. Further, the conductive water repellent layer is required to be porous as described above. For example, a fiber aggregate such as a microporous film formed of a material applied to a conductive filler, a nonwoven fabric formed of a conductive polymer material or a non-conductive polymer material can be applied. In addition, a fiber structure such as a woven fabric formed of a conductive polymer material or a non-conductive polymer material can be used.

(Negative electrode current collector layer)
The negative electrode current collecting layer 21 is not particularly limited as long as it has conductivity and does not leak the electrolyte solution outside the air battery. Examples thereof include stainless steel (SUS), copper, copper alloy, and other metal surfaces plated with corrosion-resistant metal.

(Spring)
The spring 22a is not particularly limited as long as it functions as a positive electrode current collector. For example, a material made of a metal such as stainless steel (SUS), copper, or nickel can be used. In the present embodiment, the spring 22a is used as an example, but the present invention is not limited to such an elastic body. That is, any material that functions as the conductive liquid-tight ventilation layer may be used, and it may be replaced with an inelastic material having the same shape as the spring 22a and having a current collecting function.

In the present embodiment, since the following configurations (1) to (4) are provided, the conductive path can be made thicker and shorter, and the internal resistance can be reduced.
(1) The electroconductive liquid-tight ventilation layer which is laminated | stacked on the positive electrode layer of a 1st air battery and is located in the reverse side to an electrolyte layer with respect to a positive electrode layer is provided. This conductive liquid-tight air-permeable layer contains a conductive material having water repellency, and the conductive material having water repellency is obtained by subjecting microporous carbon to fluorine treatment. Furthermore, the positive electrode layer of the first air battery is electrically connected to the negative electrode layer of the adjacent second air battery via the conductive liquid-tight ventilation layer.
(2) A flow path through which oxygen-containing gas flows is formed between the conductive liquid-tight ventilation layer laminated on the positive electrode layer of the first air battery and the negative electrode layer of the adjacent second air battery. ing.
(3) The flow path is not a conductive porous body in the flow path, but has a metal spring. Further, the layer thickness direction in the air cell, a row flat conductive path direction in the assembled battery.
(4) Since the conductive liquid-tight air-permeable layer is a conductive water-repellent layer having electrical conductivity and water-tight air permeability, a normal aqueous solution can be applied as the liquid contained in the electrolyte layer.

[Second Embodiment]
FIG. 2 is a cross-sectional view illustrating a schematic configuration of the assembled battery according to the second embodiment. In addition, the arrow shown in FIG. 2 has shown the conduction path direction. Moreover, about the thing equivalent to what was demonstrated in 1st Embodiment, the code | symbol same as them is attached | subjected and description is abbreviate | omitted.

  As shown in FIG. 2, the assembled battery 1 ′ of this embodiment is different from the assembled battery 1 of the first embodiment described above in the configuration of the positive electrode current collecting member and the conductive water repellent layer. That is, in the present embodiment, a stainless steel (SUS) mesh 22b is applied as a conductive porous body which is an example of a positive electrode current collecting member. Further, as the conductive water repellent layer 14, a layer obtained by subjecting a mixture of a non-woven olefin resin and carbon fiber 14a to a fluorination treatment is applied.

  As the conductive porous body 22b, a particle aggregate such as a metal powder sintered body can be applied. In addition, fiber assemblies such as non-woven fabrics such as metal fibers, carbon fibers, and conductive resin fibers, and fiber structures such as woven fabrics and meshes such as metal fibers, carbon fibers, and conductive resin fibers can also be applied. Furthermore, perforated plates such as punching metal and expanded metal can also be applied. However, it is not limited to these, A conventionally well-known current collection member can be applied suitably.

In the present embodiment, since the following configurations (1) to (4) are provided, the conductive path can be made thicker and shorter, and the internal resistance can be reduced.
(1) The electroconductive liquid-tight ventilation layer which is laminated | stacked on the positive electrode layer of a 1st air battery and is located in the reverse side to an electrolyte layer with respect to a positive electrode layer is provided. This conductive liquid-tight ventilation layer contains a water repellent material and a conductive material. That is, a olefin resin non-woven fabric mixed with carbon fiber and subjected to fluorine treatment is applied. Furthermore, the positive electrode layer of the first air battery is electrically connected to the negative electrode layer of the adjacent second air battery via the conductive liquid-tight ventilation layer.
(2) A flow path through which oxygen-containing gas flows is formed between the conductive liquid-tight ventilation layer laminated on the positive electrode layer of the first air battery and the negative electrode layer of the adjacent second air battery. ing.
(3) The flow path has a stainless steel (SUS) mesh which is an example of a conductive porous body in the flow path. Furthermore, it is the line a flat conductive path direction in the layer thickness direction and the battery pack in the air cells.
(4) Since the conductive liquid-tight air-permeable layer is a conductive water-repellent layer having electrical conductivity and water-tight air permeability, a normal aqueous solution can be applied as the liquid contained in the electrolyte layer.

[Third Embodiment]
FIG. 3 is a cross-sectional view showing a schematic configuration of the assembled battery according to the third embodiment. In addition, the arrow shown in FIG. 3 has shown the conduction path direction. Moreover, about the thing equivalent to what was demonstrated in 1st Embodiment, the code | symbol same as them is attached | subjected and description is abbreviate | omitted.

  As shown in FIG. 3, the assembled battery 1 ″ according to the present embodiment is different from the assembled battery 1 according to the first embodiment described above in the configuration of the positive electrode current collecting member and the conductive water repellent layer. That is, in the present embodiment, a stainless steel (SUS) mesh 22b is applied as the positive electrode current collecting member. Further, as the conductive water repellent layer 14, a layer obtained by subjecting a mixture of a non-woven olefin resin and carbon particles 14b to a fluorination treatment is applied.

In the present embodiment, since the following configurations (1) to (4) are provided, the conductive path can be made thicker and shorter, and the internal resistance can be reduced.
(1) The electroconductive liquid-tight ventilation layer which is laminated | stacked on the positive electrode layer of a 1st air battery and is located in the reverse side to an electrolyte layer with respect to a positive electrode layer is provided. This conductive liquid-tight ventilation layer contains a water repellent material and a conductive material. That is, a olefin resin non-woven fabric mixed with carbon particles and subjected to fluorine treatment is applied. Furthermore, the positive electrode layer of the first air battery is electrically connected to the negative electrode layer of the adjacent second air battery via the conductive liquid-tight ventilation layer.
(2) A flow path through which oxygen-containing gas flows is formed between the conductive liquid-tight ventilation layer laminated on the positive electrode layer of the first air battery and the negative electrode layer of the adjacent second air battery. ing.
(3) The flow path has a stainless steel (SUS) mesh which is an example of a conductive porous body in the flow path. Furthermore, it is the line a flat conductive path direction in the layer thickness direction and the battery pack in the air cells.
(4) Since the conductive liquid-tight air-permeable layer is a conductive water-repellent layer having electrical conductivity and water-tight air permeability, a normal aqueous solution can be applied as the liquid contained in the electrolyte layer.

  Although the contents of the present invention have been described with reference to the embodiments, the present invention is not limited to these descriptions, and it is obvious to those skilled in the art that various modifications and improvements can be made.

  For example, details of the configuration of the conductive water repellent layer and the positive electrode current collector can be changed. In addition, the configuration of each embodiment may be a combination other than the above-described embodiments.

  The entire contents of Japanese Patent Application No. 2011-201704 (filing date: September 15, 2011) are cited herein.

  According to the present invention, an assembled battery including a plurality of air batteries having a positive electrode layer, an electrolyte layer, a negative electrode layer, and a conductive liquid-tight ventilation layer has the following configurations (1) and (2). It was supposed to be. Therefore, an assembled battery that can reduce internal resistance can be provided. (1) A flow path is provided between the conductive liquid-tight ventilation layer in the first air battery and the negative electrode layer in the second air battery adjacent to the first air battery, and allows the oxygen-containing gas to flow therethrough. ing. (2) The first air battery is electrically connected to the negative electrode layer in the second air battery via the conductive liquid-tight ventilation layer.

1, 1 ′, 1 ″ assembled battery 10, 10 ′ air battery 11 negative electrode layer 12 positive electrode layer 13 electrolyte layer 14 conductive liquid-tight ventilation layer (conductive water repellent layer)
14a Carbon fiber 14b Carbon particles 21, 21 ', 21''Negative electrode current collecting layer 22a Spring 22b Conductive porous body (mesh)
AP Oxygen-containing gas flow path

Claims (10)

1. A positive electrode layer, an electrolyte layer laminated on the positive electrode layer, a negative electrode layer laminated on the electrolyte layer, a laminated layer on the positive electrode layer, and positioned opposite to the electrolyte layer with respect to the positive electrode layer A plurality of air batteries comprising a conductive liquid-tight ventilation layer ,
   Interposed between the conductive liquid-tight ventilation layer in the first air battery and the negative electrode layer in the second air battery adjacent to the first air battery, a flow path for circulating an oxygen-containing gas is provided,
   The assembled battery, wherein the first air battery is electrically connected to a negative electrode layer in the second air battery via the conductive liquid-tight ventilation layer.
2. The flow path includes a conductive porous body inside,
   Assembled battery according to claim 1 in which the conductive path direction in the battery pack and the layer thickness direction in the air battery, characterized in that it is configured in a flat row.
3. The assembled battery according to claim 1, wherein the conductive liquid-tight ventilation layer is a conductive water-repellent layer having conductivity and water-tight ventilation.
4. The assembled battery according to claim 3 , wherein the conductive water-repellent layer contains a conductive material having water repellency and at least one of a water-repellent material and a conductive material.
5. The assembled battery according to claim 3 or 4 , wherein the conductive water-repellent layer contains at least one selected from the group consisting of a microporous film, a fiber assembly, and a fiber structure.
6. The assembled battery according to claim 4 , wherein the conductive material is at least one of a fibrous conductive material and a particulate conductive material.
7. The assembled battery according to claim 4 or 6 , wherein the conductive material contains at least one of carbon and metal.
8. The assembled battery according to claim 4 , wherein the water repellent material contains at least one of an olefin resin and a fluorine resin.
9. The assembled battery according to claim 2 , wherein the conductive porous body is at least one selected from the group consisting of a particle aggregate, a fiber aggregate, a fiber structure, and a porous plate.
10. The assembled battery according to claim 2 or 9 , wherein the conductive porous body contains at least one of carbon and metal.

Images